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Related Concept Videos

Cycloaddition Reactions: Overview01:16

Cycloaddition Reactions: Overview

Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction01:16

[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction

The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

Cycloaddition Reactions: MO Requirements for Thermal Activation

Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry01:28

Diels–Alder Reaction Forming Cyclic Products: Stereochemistry

The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry01:29

Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry

Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.

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Related Experiment Video

Updated: May 16, 2026

Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of α-Imino γ-Lactones and Alkylidene Pyrazolones
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Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of α-Imino γ-Lactones and Alkylidene Pyrazolones

Published on: February 7, 2019

Stereoselective Higher-Order [10+4]- and [10+6] Cycloadditions Between Two Highly Unsaturated and Ambiphilic

Jonas Faghtmann1, Anne Kristensen1, Fabien Fritz1

  • 1Department of Chemistry, Aarhus University, Aarhus C, Denmark.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|May 14, 2026
PubMed
Summary

This study addresses controlling selectivity in higher-order cycloadditions (HOCs) involving complex molecules. Researchers optimized reactions to selectively form desired [10+4] or [10+6] cycloadducts.

Keywords:
3‐oxidopyridinium betaineDFT calculationsasymmetric organocatalysishigher‐order cycloaddition

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Area of Science:

  • Organic Chemistry
  • Catalysis
  • Stereochemistry

Background:

  • Higher-order cycloadditions (HOCs) present significant challenges in controlling multiple selectivity layers (peri-, regio-, diastereoselectivity, and enantioselectivity).
  • Controlling selectivity is particularly difficult when HOCs involve two highly unsaturated and ambiphilic π-addends.

Purpose of the Study:

  • To investigate the complexity of enantioselective aminocatalyzed HOCs between isobenzofulvenes (10π-components) and 3-oxidopyridinium betaines (4π- or 6π-components).
  • To explore the formation of [10+4] cycloadducts and regioisomeric [10+6] cycloadducts, including unprecedented 6π-component reactions.

Main Methods:

  • Enantioselective aminocatalyzed reactions.
  • Experimental investigations combined with Density Functional Theory (DFT) calculations.
  • Optimization of reaction conditions to control selectivity.

Main Results:

  • The reaction produces an allowed [10+4] cycloadduct and two forbidden regioisomeric [10+6] cycloadducts.
  • Demonstrated successful optimization to selectively form either the [10+4] cycloadduct or the [10+6] cycloadducts.
  • Elucidated the origins of selectivity through experimental and computational studies.

Conclusions:

  • Achieved control over peri- and regioselectivity in complex HOCs involving unsaturated, ambiphilic π-addends.
  • Developed methods for selective synthesis of [10+4] and [10+6] cycloadducts.
  • Provided insights into the mechanistic pathways governing selectivity in these challenging cycloadditions.